Alkyloxalyl amino-s-triazines

ABSTRACT

Compounds having the formula   WHEREIN R is chlorine, methylthio or ethylthio, R1, R2, and R3 are alkyl, and their uses as herbicides.

nlted States Patent 1191 1111 3,856,73 MacDonald 1451 Dec. 24, 1974 ALKYLOXALYL AMlNO-S-TRIAZINES Primarv E.\'aminerJ0hn M. Ford 75 I t. Al A.M D ld,Alb ,Clf. 1 men or an ac ona any M Attorney, Agent, or Fzrm-Edwm H. Baker [73] Assignee: Stauifer Chemical Company, New

York 57 ABSTRACT [22] Flledz Apr. 2, 1973 Compounds having the formula [21] Appl. N0.: 347,296 Ni 52 us. Cl....-. 260/249.8, 71/93 0 O 51 Int. Cl C07d 55/20 N [58] Field of Search 260/249.8 l &2

[56] References Cited whereln R is Ci'llOIlflB, methylthlo or ethylthio, R R UNITED STATES PATENTS and R are alkyl, and their uses as herbicides. 3,786,053 Ill 974 Chapman et a1 260/2498 3,819,626 6/1974 Kobzina 260/249.8 7 (11191191151139 Drawmgs 1 ALKYLOXALYL AMINO-S-TRIAZINES This invention relates to certain novel alkyloxalylamino substituted s-triazines which are useful as herbicides.

The compounds of the present invention have the formula where R is chlorine, methylthio or ethylthio, preferably chlorine or methylthio; R is alkyl having 1 to 4 carbon atoms, preferably having 1 to 2 carbon atoms; R is alkyl having 1 to 4 carbon atoms, preferably having 1 to 2 carbon atoms, and R is alkyl having 1 to 4 carbon atoms, preferably having 1 to 3 carbon atoms.

The alkyl groups are either straight, branched or cyclic.

The compounds of this invention are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

An herbicide is used herein to mean a compound which controls or modifies the growth of plants. By a growth controlling amount is meant an amount of compound which causes a modifying effect upon the growth of plants. Such modifying effects include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation,

stunting, tillering, stimulation, dwarfing and the like. By plants, it is meant germinating seeds, emerging seedlings, and established vegetation including the roots and above-ground portions.

The compounds of the present invention can be prepared by the following reaction:

Generally, about a mole amount of the oxalyl chloride reactant and about a mole amount of the s-triazine reactant are reacted in a solvent such as perchloroethylene at reflux temperature for about 4 hours. The reaction mixture is filtered to remove solids and the solvent is vacuum stripped at reduced pressure to yield the desired product.

EXAMPLE 2-chloro-4-(ethyl oxalyl) ethylamino-6-isopropylamino-s-triazine LII C) NN NH l0.8 grams (0.05 mols) of 2-chloro-4-ethylamino-6- isopropylamino-s-triazine and 6.9 grams (0.05 mole) of ethyl oxalyl chloride are combined with ml. 1,2- dichloroethane in a 500 ml. 3-neck flask equipped with a stirrer, thermometer and reflux condenser. The mixture is reflux for 9 hours. It is then cooled to room temperature and filtered. Evaporation of the solvent leaves the desired product, a viscous light amber liquid. The structure is confirmed by n.m.r.

The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used through the remainder of the application.

TABLE I R 0 uns 1 3 COMPOUND N or NUMBER R R R R m.p

l. chlorine methyl ethyl i-propyl l 4960 2. methylthio ethyl ethyl i propyl l 5153 3. methylthio ethyl i-propyl i-propyl l 5160 4. chlorine methyl ethyl ethyl 5. methylthio methyl ethyl ethyl 6. methylthio ethyl ethyl ethyl 7. chlorine methyl ethyl ipropyl 1.5097

8. methylthio methyl ethyl i-propyl 9. methylthio methyl ethyl tbutyl 1.5280 10. methylthio ethyl ethyl t-butyl l.5l97 l l. chlorine methyl i-propyl i-propyl l2. chlorine ethyl i'propyl i-propyl l3. methylthio methyl i-propyl i-propyl l4. chlorine ethyl ethyl ethyl 1 l8- l22C. *15. chlorine ethyl ethyl i-propyl Prepared in the Example.

Herbicidal Screening Tests As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention are tested as herbicides in the following manner.

Pre-emergence herbicide test.

On the day preceding treatment, seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds used are hairy crabgrass (Digitaris 'sanguinalis (L.) Scop. yellow foxtail (Setaria glauca (L.) Beauv.), watergrass (Echinochloa crusgalli (L.) Beauv.), California red oat (Avena sativa (L.), redroot pigweed (Amaranthus retroflexus (L.), Indian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus (L.). Ample seeds are planted to give about 20 to 50 seedlings per row, after emergence, depending upon the size of the plants. The flats are watered after planting.

The spraying solution is prepared by dissolving 50 mg. of the test compound in 3 ml. of solvent, such as acetone, containing 1% Tween 20 (polyoxyethylene sorbitan monolaurate). The following day each flat is sprayed at the rate of 20 pounds of the candidate compound per 80 gallons of solution per acre. An atomizer is used to spray the solution onto the soil surface. The flats are placed in a greenhouse at 80F. and watered regularly. Two weeks later the degree of weed control is determined by comparing the amount of germination and growth of each weed in the treated flats with the same weeds in several untreated control flats. The results of the test are reported in Table II using the folowing rating system:

TABLE II Tween 20 (polyoxyethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5% and the rate would be approximately pounds per acre if all of the spray was retained on the plant and the soil, but some spray is lost so it is estimated that the application rate is approximately 12.5 pounds per acre.

Beans are used to detect defoliants and plant growth regulators. The beans are trimmed to two or three plants per flat by cutting off the excess weaker plants several days before treatment. The treated plants are placed back in the greenhouse and care is taken to avoid sprinkling the treated foliage with water for three Rated as percent injury 0 no injury 100 complete control PRE-EMERGENCE ACTIVITY RATE 2O LBSJA Com- Crab Water Wild Curled pound Number grass Foxtail grass oat Pigweed Mustard dock l. 95 90 70 80 70 I00 70 2. 95 7O 5O 6O 80 I00 95 3. 90 70 8O 7O 98 100 90 4. I00 97 95 I00 I00 I00 I00 5. 98 I00 98 99 I00 100 100 6. 100 95 95 80 I00 90 100 7. 95 98 98 I00 100 I00 I00 8. 98 98 95 I00 I00 I00 lOO 9. 98 95 95 I00 I00 I00 I0. 99 99 I00 20 I00 I00 100 ll. 80 7O 8O 80 99 I00 80 I2. 80 7O 8O 90 lOO I00 100 I3. I00 99 95 90 I00 I00 100 l4. 98 I00 80 I00 I00 I00 80 I5. I00 I00 100 I00 I00 100 98 Post-emergence herbicide test.

Seeds of five weed species previously recited, including hairy crabgrass, watergrass, California red oats, Indian mustard, and curly dock and one crop, pinto beans (Phaseolus vulgaris), are planted in flats as described above for pre-emergence screening. The flats days after treatment. Water is applied to the soil by means of a slow stream from a watering hose taking care not to wet the foliage.

Injury rates are recorded 14 days after treatment.

I The rating system is the same as described above for the preemergence test where 0 no injury and 100 complete control. The results are reported in Table III.

TABLE III POST-EMERGENCE ACTIVITY RATE 20 LBS/A. COM- CRAB WATER RED CURLED PINTO POUND NUMBER GRASS GRASS OATS MUSTARD DOCK BEANS l. I00 90 I00 I00 I00 I00 2. I00 95 100 I00 95 I00 3. I00 95 I00 I00 95 lOO 4. I00 I00 I00 lOO I00 100 5. I00 98 I00 I00 I00 I00 6. I00 97 lOO I00 I00 7. I00 I00 I00 I00 I00 I00 8. I00 98 I00 100 98 l0() 9. I00 98 I00 I00 I00 100 I0. H10 100 I00 lOO I00 ll. 80 97 lOO I00 I00 100 I2. I00 100 I00 I00 99 I00 13. I00 99 I00 I00 I00 14. I00 I00 I00 I00 100 I00 15. I00 lOO I00 lOO I00 100 are placed in the greenhouse at 7285F. and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plant are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 5 'ml. of acetone containing 1% The compounds of the present invention are used as pre-emergence and post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds herein defined are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds may be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. Preferred formulations for both preand postemergence herbicidal applications are wettable powders, emulsifiable concentrates and granules. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. The amount applied depends upon the nature of the seeds or plants to be controlled and the rate of application varies from 1 to approximately 50 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fullers earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient by weight and usually also contain a small amount of wetting, dispersing or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or many also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5 to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations, wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fullers earth, bentonite clays, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 5 to about 25% of active ingredient and may also contain small amounts of other ingredients which may include surface-active agents such as wetting agents, dispersing agents or emulsifiers; oils such as heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydric alcohols; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1 to by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating applications.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5 to about of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene or other organic solvents; Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dusts and liquid compositions can be applied to the plant by the use of powerdusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to convention methods and are distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the above-described compounds include, for example, 2,4-dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2,4-bis(S-methoxypropylamino)-6- methylthio-s-triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, and 2-ethylamino-4- isopropylamino-6-methylmercapto-s-triazine; urea derivatives, such as 3-(3,4-dichlorophenyl)-l,l-dimethyl urea and 3-(p-chlorophenyl)-l,l-dirnethyl urea; and acetamides such as N,N-diallyl-B-chloroacetamide, and the like; benzoic acids such as 3-amino-2,5- dichlorobenzoic; thiocarbamates, such as S-propyl dipropylthiocarbamate, S-ethyldipropylthiocarbamate, S-ethyl cyclohexylethyl thiocarbamate, S-ethyl hexahydro-lH-azepine-l-carbothioate and the like; 4- (methylsulfonyl)-2,6-dinitro-N,N-substituted anilines, such as 4-(methylsulfonyl)-2,6-dinitro-N,N-di-n-propyl aniline, 4-trifluoromethyl-2,6-dinitro-N,N-substituted anilines, such as 4-trifluoromethyl-2,6-dinitro-N,N-din-propyl anilines and 4-trifluoromethyl-2,6-dinitro-N- ethyl-N-n-butyl aniline.

Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed is readily determinable by those skilled in the art.

R AN

where R is chlorine or methylthio; R is alkyl having 1 to 2 carbon atoms; R is alkyl having I to 2 carbon atoms; and R is alkyl having 1 to 3 carbon atoms.

3. The compound of claim 1 in which R is chlorine, R is ethyl, R is ethyl and R is isopropyl.

4. The compound of claim 1 in which R is chlorine, R is ethyl, R is ethyl and R is ethyl.

5. The compound of claim 1 in which R is methylthio, R is ethyl, R is ethyl and R is ethyl.

6. The compound of claim 1 in which R is chlorine, R is methyl, R is ethyl and R is isopropyl.

7. The compound of claim 1 in which R is chlorine, R is methyl, R is ethyl and R is ethyl. 

1. A COMPOUND OF THE FORMULA
 2. A compound of the formula
 3. The compound of claim 1 in which R is chlorine, R1 is ethyl, R2 is ethyl and R3 is isopropyl.
 4. The compound of claim 1 in which R is chlorine, R1 is ethyl, R2 is ethyl and R3 is ethyl.
 5. The compound of claim 1 in which R is methylthio, R1 is ethyl, R2 is ethyl and R3 is ethyl.
 6. The compound of claim 1 in which R is chlorine, R1 is methyl, R2 is ethyl and R3 is isopropyl.
 7. The compound of claim 1 in which R is chlorine, R1 is methyl, R2 is ethyl and R3 is ethyl. 